Compositions containing aminopolyureylene resin

ABSTRACT

Compositions comprising a mixture of an aminopolyureylene resin having a molecular weight in the range of about 300 to 100,000 and an active material selected from the group of antibacterial materials, tarnish inhibitors, ultra violet absorbers, fluorescent brighteners, bluing agents and skin treating materials, the weight ratio of resin to active material being effective to improve the properties of the active material and being selected from the range of 1:1 to 20:1. Preferred compositions comprise 2% to 99% by weight of a water-soluble organic detergent, 0.05% to 5% by weight of aminopolyureylene resin and 0.05 to 5% by weight of active material.

This is a continuation, of application Ser. No. 308,883 filed Nov. 22,1972, now abandoned which is a division of application Ser. No. 90,154,filed Nov. 16, 1970, now U.S. Pat. No. 3,726,815.

The invention relates to improved compositions comprising awater-soluble and/or water-insoluble active material having the capacityto impart a residual characteristic to surfaces treated therewith suchas antibacterial compounds, tarnish inhibitors, ultra-violet absorbers,fluorescent brighteners, bluing agents and skin treating materials andan aminopolyureylene (APU) resin in an amount effective to enhance theeffects of the active materials. The APU resins appear to enhance thedeposition and/or retention of the water-soluble and water-insolubleactive substances on the surfaces contacted therewith.

The capacity of the APU resin to improve the effectiveness of the activematerials on surfaces contacted therewith surprisingly is maintained inthe presence of water-soluble organic detergents and, therefore,detergent compositions containing the mixture of active material and APUresin represent preferred embodiments. Such detergent compositionsinclude dishwashing detergents, shampoos, laundry detergents,hard-surface cleaners and toilet bars. The effectiveness of the APUresins in the presence of minor and major amounts of water-solubleorganic detergents is surprising because the effectiveness of the activematerials is due to the deposition and/or retention of the activematerials on surfaces contacted therewith and detergents normally tendto minimize deposition and retention of such materials on the washedsurfaces. Thus, usually only a small percentage of the active materialsin a detergent composition is actually retained on a particular surfaceor substrate after washing and, optionally, rinsing. Accordingly, toachieve a particular level of activity, the concentration of activematerial must be increased-with an attendant increase in cost--when usedas a component in a detergent composition.

While the mechanism by which the improved effects are obtained is notunderstood, it appears that the APU resin may unite either with theactive material or the contacted surface to increase the affinity of theactive material for the surface. In many cases, an increase in theweight of active material retained by the surface has beenquantitatively verified. However, no absolute mechanism has been definedand the invention is not limited to any particular theory.

Generally, the improved compositions of this invention consistessentially of a mixture of an aminopolyureylene resin having amolecular weight in the range of about 300 to 100,000 and awater-soluble or water-insoluble active material having the capacity toimpart a residual property to surfaces treated therewith and selectedfrom the group consisting of (A) antibacterial compounds, (B) tarnishinhibitors, (C) ultra-violet absorbers, (D) optical brighteners, (E)bluing agents and (F) skin-treating compounds, the weight ratio of resinto active material being effective to improve the effects of the activematerial and selected from the range of 1:1 to 20:1 preferably 1:1 to5:1. Preferred compositions are detergent compositions comprising 2% to99% by weight of a water-soluble, organic detergent, 0.05% to 5% byweight of aminopolyureylene resin and about 0.05 to 5% by weight ofactive material.

Also, within the scope of the invention is a method for improving theeffectiveness of active materials on surfaces contacted therewith whichcomprises contacting the surface with a water solution or dispersion ofthe active material and an effective amount of the aminopolyureyleneresin sufficient to improve the effect of the active material retainedon the treated surface after the contacting solution is removed.

The APU resins suitable for use in the described compositions and methodhave a molecular weight in the range of about 300 to 100,000 and arecharacterized by the following repeating unit:

    --(CH.sub.2).sub.n X--(CH.sub.2).sub.n NHC(Y)NH--

wherein X is NH, N-C₁ to C₂₂ alkyl, ##STR1## Y is O or S, and n is 2 or3. Such APU resins and their cosmetic effectiveness are set forth in thecopending application of Paul Grand entitled "Cosmetic Compositions"filed of even date herewith.

Thus, suitable APU resins include both the polyurea- and thepolythiourea-containing compounds. Preferred APU resins have a repeatingunit where Y is oxygen, n is 3, and X is selected from the groupconsisting of N--C₁₈ alkyl and ##STR2##

Generally, the number of repeating units in the resin will be sufficientto yield a polymer having a molecular weight in the range of about 300to 100,000. Preferred APU resins have an average molecular weight in therange of 1,000 to 20,000 and a particularly preferred resin is thereaction product of equimolar quantities of N-methyl,bis(3-amino-propyl) amine and urea having a molecular weight of about4,300.

The molecular weight of the APU resins is based upon aqueous gelpermeation chromatographic analysis. The separation is carried out inoxalic acid solution, adjusted to pH 3.5, on three Corningcontrolled-pore glass columns (nominal pore sizes 175,125 and 75 A) inseries. Detection is by differential refractometer. Reference compoundsare dextran polysaccharides of molecular weights of 150,000, 110,000,40,000, 20,000 and 10,000 and sucrose and galactose.

The APU resins which can be used in the compositions of this inventionare prepared by reacting, for example, 145 grams of N-methylbis(3-aminopropyl) amine (1.0 mole) and 60 grams of urea (1.0 mole) in a3-necked flask equipped with a therometer, mechanical stirrer,condenser, and nitrogen sparge tube. Nitrogen is bubbled slowly throughthe solution throughout the course of the reaction. The solution isheated to 140° C. over a 20-minute interval where ammonia begins toevolve. The solution is further heated to 250° C. over a 30-minuteinterval and allowed to cool. The product is a hard, resinous powder(Resin A) having a molecular weight of about 4,300. The secondary amineanalogues can be made by the above process if bis(3-aminopropyl) amineor bis(2-aminoethyl) amine are reacted with urea or thiourea. Thepiperazine analogues are made by reactingN,N'-di(3-aminopropyl)piperazine or N,N'-di(2-aminoethyl)piperazine withurea or thiourea. The N--C₁ to C₂₂ alkyl analogues are prepared byreacting N--C₁ to C₂₂ alkyl bis(3-aminopropyl) amine or N--C₁ to C₂₂alkyl bis(2-aminoalkyl) amine with urea or thiourea. Additionalanalogues are prepared by the following reactions: ##STR3##

The preparation of the remaining analogues is well within the skill ofthe art following the above techniques.

The active materials which are potentiated by the APU resin are wellknown and have been used for treating surfaces and substrates to impartcertain residual characteristics to the contacted surfaces. The treatedsurfaces or substrates include proteinaceous materials such as hair andskin, textiles such as cotton, rayon and synthetic fibers, andporcelain, wood, plastic and metal. Such active materials may bewater-soluble such as cetyl dimethyl benzyl ammonium bromide and gelatinor water-insoluble such as zinc 2-pyridinethiol-1-oxide and opticalbrighteners. To facilitate activity and utility, the water-insolublematerials are usually in the form of finely divided particles having adiameter in the range of about 0.5 to 50 microns. Suitable activematerials include antibacterial compounds, tarnish inhibitors,ultra-violet absorbers, optical brighteners, bluing agents and skintreating materials such as hydrolyzed proteins, silicones andpolyacrylamides.

Antibacterial compounds which may be used in the compositions includewater-soluble and water-insoluble salts of 2-pyridinethiol-1-oxide,substituted salicylanilides, substituted carbanilides, halogenatedbisphenols, mono-higher alkyl quaternary ammonium salts, and 5,7diiodo-8-hydroxyquinoline.

Preferred antibacterial compounds include the water-insoluble salts,e.g., zinc, cadmium, zirconium, tin and aluminum, and water-solublesalts, e.g., sodium and potassium, of 2-pyridinethiol-1-oxide which hasthe following structural formula in tautomeric form. ##STR4## The zincand sodium salts of 2-pyridinethiol-1-oxide are particularly preferred.

Other suitable antibacterial compounds are the substituted bisphenolshaving the formula ##STR5## wherein X is a halogen such as chlorine orbromine, n is 1-3 and R is an alkylene of 1-4 carbon atoms or divalentsulfur. Typical compounds include bis(3,5,6-trichloro-2-hydroxyphenyl)methane or sulfide, bis(5-chloro-2-hydroxyphenyl)methane andbis(3,5-dichloro-2-hydroxyphenyl)methane or sulfide.

Suitable antibacterial substituted salicylanilides have the structuralformula ##STR6## wherein Y is hydrogen, halogen, or trifluoromethyl andZ is hydrogen or halogen. Among the suitable salicylanilides are3,4',5'-tribromosalicylanilide;5--bromosalicyl--3,5--di(trifluoromethyl)anlide;5--chlorosalicycl--3,5--di(trifluoromethyl)anlide;3,5--dichlorosalicyl--3,4--dichloroanilide; and5--chlorosalicyl--3--trifluoromethyl--4--chloroanilide. These and otheruseful salicylanilides are disclosed in U.S. Patent No. 2,703,332.

Satisfactory substituted carbanilides have the following generalstructure ##STR7## wherein Y is hydrogen, halogen, or trifluoromethyl, Wis halogen or ethoxy, and W₁ is hydrogen or halogen. Included among thesuitable carbanilides are 3,4,4'-trichlorocarbanilide;4,4'-trifluoromethyl-3'4,4'-trichlorocarbanilide;3,3'-bis(trifluoromethyl--4--ethoxy--4'--chlorocarbanilide; and3,5--bis(trifluoromethyl)--4'--chlorocarbanilide.

Other antibacterial materials are the mono-higher-alkyl quaternaryammonium salts having the following structural formula: ##STR8## whereinR₁ is C₈ to C₂₂ alkyl, R₂ and R₃ are each C₁ -C₃ alkyl, R₄ is C₁ -C₃alkyl or benzyl and A is an anion selected from the group consisting ofchlorine, bromine, iodine, and methosulfate. A preferred compound iscetyl trimethyl ammonium bromide.

Additional useful antimicrobial compounds include 5,7-diiodo-8-hydroxyquinoline, 1,6-di(4'chlorophenyl-diquanado)hexane, and5-chloro-2(2,4-dichlorophenoxy)phenol, C₈ to C₂₂ isoquinolinium halides,such as lauryl isoquinolinium bromide, and C₈ -C₂₂ alkyl pyridiniumhalide.

The tarnish inhibitors potentiated by APU resins include, for example,benzotriazole and ethylenethiourea.

Ultraviolet absorbers potentiated by APU resins have the structuralformula ##STR9## where X, Y, and Z are selected from the groupconsisting of hydrogen, hydroxy, C₁ to C₈ alkoxy and carboxy, at leastone of said X, Y, and Z being oxy. Preferred compounds include2-hydroxy-4-n-octoxy-benzophenone and2-hydroxy-4-methoxy-2'-carboxy-benzophenone.

The optical or fluoroescent brightener active materials which arepotentiated by the APU resins are selected from the group consisting ofstilbene disulfonates, quaternized aminoalkyl substituted phenylsulfonamides of aryl pyrazolines, substituted styrylnaphth oxazoles, andsubstituted aminocoumarins.

Suitable stilbene disulfonate fluorescent brighteners have the formulaformula ##STR10## wherein X is OH, ##STR11## Suitable compounds aredisodium 4,4' bis [4-anilino-6-methoxyanilino-s-triazin-2yl amino]-2,2'stilbene disulfonate and disodium 4,4' bis(4,6 dianilino-s-triazin-2ylamino) 2,2' stilbene-disulfonate.

Suitable quaternized aminoalkyl substituted phenyl sulfonamides of arylpyrazoline have the following formula: ##STR12## Wherein X is hydrogen,phenyl, or halogenated phenyl with not more than one X being hydrogenand Y is a quaternized ##STR13## wherein R is C₁ -C₄ alkyl and R₁ and R₂are each elected from the group consisting of hydrogen and C₁ -C₃ alkyl.A typical compound is quaternized-1-p(sulfonyl-γ-dimethyl aminopropylamido)-phenyl-3-p-chlorophenyl pyrazoline.

Suitable oxazole fluorescent brighteners have the structural formula:##STR14## wherein A and B are different and represent oxygen andnitrogen, and R represents individually hydrogen, alkyl groups having 1to 6 carbon atoms, chlorine or fluorine. A preferred oxazole brighteneris 2-styrlnaphth (1,2-d) oxazole.

Additional fluorescent brighteners potentiated by APU resin are thewater-soluble substituted aminocoumarins having the following structuralformula: ##STR15## wherein R is hydrogen or C₁ -C₂ alkyl. A preferredcompound is 4 methyl, 7 dimethyl amino coumarin.

A bluing material which is potentiated by APU resin is ultramarine blue.This is a well-known blue pigment occurring naturally as mineral thelapis lazuli. It can be made, for example, by igniting a mixture ofkaolin, sodium carbonate or sulfate, sulfur, and carbon. It is insolublein water and is stable when in contact with bleaching agents, alkali,and light. Details for synthetic ultramarines are given in the text"Ultramarines, Their History and Characteristic," Reckitts (Colours)Ltd., Hull, England. Preferred are micropulverized, syntheticultramarine blues, particularly grades RS4-RS8 provided by Reckitts. Thepigment is in the form of particles substantially all of which exhibit adiameter of less than about 0.05 millimeter, and is characterized by theability to impart a faint blue visible shade to fabrics treatedtherewith without staining such fabrics when used at recommendedconcentration and fashion, being generally considered to benon-substantive, or at least non-accumulative, on fabrics.

The skin-treating materials which are enhanced by the APU resins are thewater-soluble, substantive proteins. Such proteins are substantive tothe hair and skin in the presence of detergents. Suitable proteins arewater-soluble polypeptides, having a molecular weight in the range ofabout 120 (amino acid) to about 20,000, preferably from about 800 to12,000. Such polypeptides are obtained by hydrolysis of proteinmaterials such as hides, gelatin, collagen, and the like, with collagenprotein being preferred, using well-known processes. During hydrolysisthe protein materials are gradually broken down into their constituentpolypeptides and amino acids by prolonged heating with acids, e.g.,sulfuric acid, or alkalis, e.g., sodium hydroxide, or treatment withenzymes, e.g., peptidases. First, high molecular weight polypeptides areformed, and as hydrolysis proceeds these are converted progressively tosimpler and simpler polypeptides, to tripeptides, dipeptides, andfinally to amino acids. It is obvious that the polypeptides derived fromproteins are complex mixtures. The preferred hydrolysates are obtainedfrom bone- or skin-derived collagen protein by enzymatic hydrolysis andare sold under the trade names "WSP-X-250" and "WSP-X-1000" of WilsonPharmaceutical and Chemical Corporation.

Other skin-treating materials whose skin-slip or anti-frictionproperties are enhanced by APU resins include ethylene oxide polymershaving a molecular weight in the range of about 500,000 to 1,000,000which are sold under the trade name "Polyox."

The water-soluble organic detergent materials which can be used informing the preferred detergent compositions of this invention may beselected from the group consisting of anionic, nonionic, amphoteric,zwitterionic, polar nonionic, and cationic detergents, and mixtures oftwo or more of the foregoing detergents.

The anionic surface-active agents include those surface-active ordetergent compounds which contain an organic hydrophobic groupcontaining generally 8 to 26 carbon atoms and preferably 10 to 18 carbonatoms in their molecular structure, and at least one water-solubilizinggroup selected from the group of sulfonate, sulfate, carboxylate,phosphonate and phosphate so as to form a water-soluble detergent.

Examples of suitable anionic detergents which fall within the scope ofthe anionic detergent class include the water-soluble salts, forexample, the sodium, ammonium, and alkylolammonium salts, of higherfatty acids or resin salts containing about 8 to 20 carbon atoms,preferably 10 to 18 carbon atoms. Suitable fatty acids can be obtainedfrom oils and waxes of animal or vegetable origin, for example, tallow,grease, coconut oil, tall oil and mixtures thereof. Particularly usefulare the sodium and potassium salts of the fatty acid mixtures derivedfrom coconut oil and tallow, for example, sodium coconut soap andpotassium tallow soap.

The anionic class of detergents also include the water-soluble sulfatedand sulfonated synthetic detergents having an alkyl radical of 8 to 26,and preferably about 12 to 22 carbon atoms. (The term alkyl includes thealkyl portion of the higher acyl radicals.)

Examples of the sulfonated anionic detergents are the higher alkylmononuclear aromatic sulfonates such as the higher alkyl benzenesulfonates containing from 10 to 16 carbon atoms in the higher alkylgroup in a straight or branched chain, for example, the sodium,potassium, and ammonium salts of higher alkyl benzene sulfonates, higheralkyl toluene sulfonates, higher alkyl phenol sulfonates and highernaphthalene sulfonates. A preferred sulfonate is linear alkyl benzenesulfonate having a high content of 3- (or higher) phenyl isomers and acorrespondingly low content (well below 50%) of 2- (or lower) phenylisomers, that is, wherein the benzene ring is preferably attached inlarge part at the 3 or higher (for example, 4, 5, 6 or 7) position ofthe alkyl group and the content of the isomers in which the benzene ringis attached in the 2 or 1 position is correspondingly low. Particularlypreferred materials are set forth in U.S. Pat. No. 3,320,174.

Other suitable anionic detergents are the olefin sulfonates, includinglong-chain alkene sulfonates, long-chain hydroxyalkane sulfonates ormixtures of alkene sulfonates and hydroxyalkane sulfonates. These olefinsulfonate detergents may be prepared in a known manner by the reactionof SO₃ with long-chain olefins containing 8 to 25, preferably 12 to 21carbon atoms and having the formula RCH═CHR₁ where R is a higher alkylgroup of 6 to 23 carbons and R₁ is an alkyl group or 1 to 17 carbons orhydrogen to form a mixture of sultones and alkene sulfonic acids whichis then treated to convert the sultones to sulfonates. Other examples ofsulfate or sulfonate detergents are paraffin sulfonates containing about10 to 20 and preferably about 15 to 20 carbon atoms, for example, theprimary paraffin sulfonates are made by reacting long-chain alphaolefins and bisulfites and paraffin sulfonates having the sulfonatedgroup distributed along the paraffin chain as shown in U.S. Pat. Nos.2,503,280; 2,507,088; 3,260,741; 3,372,188; and German Pat. No. 735,096;sodium and potassium sulfates of higher alcohols containing 8 to 18carbon atoms such as sodium lauryl sulfate and sodium tallow alcoholsulfate; sodium and potassium salts of α-sulfofatty acid esterscontaining about 10 to 20 carbon atoms in the acyl group, for example,methyl α-sulfomyristate and methyl α-sulfotallowate, ammonium sulfatesof mono- or di-glycerides of higher (C₁₀ -C₁₈) fatty acids, for example,stearic monoglyceride monosulfate; sodium and alkylolammonium salts ofalkyl polyethenoxy ether sulfates produced by condensing 1 to 5 moles ofethylene oxide with one mole of higher (C₈ -C₁₈) alcohol; sodium higheralkyl (C₁₀ -C₁₈) glyceryl ether sulfonates; and sodium or potassiumalkyl phenol polyethenoxy ether sulfates with about 1 to 6 oxyethylenegroups per molecule and in which the alkyl radicals contain about 8 toabout 12 carbon atoms.

The suitable anionic detergents include also the C₈ to C₁₈ acylsarcosinates (for example, sodium lauryl sarcosinate), sodium andpotassium salts of the reaction product of higher fatty acids containing8 to 18 carbon atoms in the molecule esterified with isethionic acid,and sodium and potassium salts of the C₈ to C₁₈ acyl N-methyl taurides,for example, sodium cocoyl methyl taurate and potassium stearoyl methyltaurate.

Anionic phosphate surfactants in which the anionic solubilizing groupattached to the hydrophobic group is an oxyacid of phosphorous are alsouseful in the detergent compositions. Suitable phosphate surfactants arethe sodium, potassium, and ammonium alkyl phosphate esters such as(R--O)₂ PO₂ M and ROPO₃ M₂ in which R represents an alkyl chaincontaining from about 8 to 20 carbon atoms or an alkyl phenyl grouphaving 8 to 20 carbon atoms and M represents a soluble cation. Thecompound formed by including about 1 to 40 moles of ethylene oxide inthe foregoing esters, for example, [R-O(EtO)n]₂ PO₂ M, are alsosatisfactory.

The particular anionic detergent salt will be suitably selected,depending upon the particular formulation and the proportions therein.Suitable salts include the ammonium, substituted ammonium (mono-, di-,and triethanolammonium), alkali metal (such as sodium and potassium) andalkaline earth metal (such as calcium and magnesium) salts. Preferredsalts are the ammonium, triethanolammonium, sodium, and potassium saltsof the higher alkyl sulfates and the C₈ to C₁₈ acyl sarcosinates.

The nonionic synthetic organic detergents are generally the condensationproduct of an organic aliphatic or alkyl aromatic hydrophobic compoundand hydrophilic ethylene oxide groups. Practically any hydrophobiccompound having a carboxy, hydroxy, amido, or amino group with a freehydrogen attached to the nitrogen can be condensed with ethylene oxideor with the polyhydration product thereof, polyethylene glycol, to forma nonionic detergent. Further, the length of the polyethenoxy chain canbe adjusted to achieve the desired balance between the hydrophobic andhydrophilic elements.

The nonionic detergents include the polyethylene oxide condensate of onemole of alkyl phenol containing from about 6 to 12 carbon atoms in astraight- or branched-chain configuration with about 5 to 30 moles ofethylene oxide, for example, nonyl phenol condensed with 9 moles ofethylene oxide, dodecyl phenol condensed with 15 moles of ethylene anddinonyl phenol condensed with 15 moles of ethylene oxide. Condensationproducts of the corresponding alkyl thiophenols with 5 to 30 moles ofethylene oxide are also suitable.

Still other suitable nonionics are the polyoxyethylene polyoxypropyleneadducts of 1-butanol. The hydrophobe of these anionics has a minimummolecular weight of 1,000 and consists of an aliphatic monohydricalcohol containing from 1 to 8 carbon atoms to which is attached aheteric chain of oxyethylene and oxypropylene. The weight ratio ofoxypropylene to oxyethylene covers the range of 95:5 to 85:15. Attachedto this is the hydrophilic polyoxyethylene chain which is from 44.4 to54.6 of the total molecular weight.

Also included in the nonionic detergent class are the condensationproducts of a higher alcohol containing about 8 to 18 carbon atoms in astraight or branched-chain configuration condensed with about 5 to 30moles of ethylene oxide. for example, lauryl-myristyl alcohol condensedwith about 16 moles of ethylene oxide.

A particularly useful group of nonionics is marketed under the tradename "Pluronics." The compounds are formed by condensing ethylene oxidewith a hydrophobic base formed by the condensation of propylene oxidewith propylene glycol. The molecular weight of the hydrophobic portionof the molecule is of the order of 950 to 4,000 and preferably 1200 to2500. The addition of polyoxyethylene radicals to the hydrophobicportion tends to increase the solubility of the molecule as a whole. Themolecular weight of the block polymers varies from 1,000 to 15,000, andthe polyethylene oxide content may comprise 20% to 80% by weight.

Zwitterionic detergents such as the betaines and sulfobetaines havingthe following formula are also useful: ##STR16## wherein R is an alkylgroup containing about 8 to 18 carbon atoms, R₂ and R₃ are each analkylene or hydroxyalkylene group containing about 1 to 4 carbon atoms,R₄ is an alkylene or hydroxyalkylene group containing 1 to 4 carbonatoms, and X is C or S:O. The alkyl group can contain one or moreintermediate linkages such as amido, ether, or polyether linkages ornonfunctional substituents such as hydroxyl or halogen which do notsubstantially affect the hydrophobic character of the group. When X isC, the detergent is called a betaine; and when X is S:O, the detergentis called a sulfobetaine or sultaine. Preferred betaine and sulfobetainedetergents are 1-(lauryl dimethylammonio) acetate, 1-(myristyldimethylammonio) propane-3-sulfonate, and1-(myristyldimethylammonio)-2-hydroxy-propane-3-sulfonate.

The polar nonionic detergents are those in which the hydrophilic groupcontains a semi-polar bond directly between two atoms, for example, N→O,P→O, As→O, and S→O. There is charge separation between the two directlybonded atoms, but the detergent molecule bears no net charge and doesnot dissociate into ions.

The polar nonionic detergents of this invention include open-chainaliphatic amine oxides of the general formula R₁ R₂ R₃ N→O. For thepurpose of this invention R₁ is an alkyl, alkenyl, or monohydroxyalkylradical having about 10 to 16 carbon atoms, R₂ and R₃ are each selectedfrom the group consisting of methyl, ethyl, propyl, ethanol, andpropanol radicals.

Other operable polar nonionic detergents are the open-chain aliphaticphosphine oxides having the general formula R₁ R₂ R₃ P→O wherein R₁ isan alkyl, alkenyl, or monohydroxyalkyl radical ranging in chain lengthfrom 10 to 18 carbon atoms, and R₂ and R₃ are each alkyl andmonohydroxyalkyl radicals containing from 1 to 3 carbon atoms.

Examples of suitable ampholytic detergents include the alkylbeta-aminopropionates, RN(H)C₂ H₄ COOM; the alkylbetaiminodipropionates, RN(C₂ H₄ COOM)₂ ; the alkyl and hydroxy alkyltaurinates, RN(CH₃)C₂ H₄ SO₃ M; and the long-chain imidazole derivativeshaving the following formulas: ##STR17## wherein R is an acylic group ofabout 7 to 17 carbon atoms, W is selected from the group of R₂ OH, R₂COOM, and R₂ OR₂ COOM, Y is selected from the group consisting of OH⁻,R₃ OSO₃ ⁻, R₂ is an alkylene or hydroxyalkylene group containing 1 to 4carbon atoms, R₃ is selected from the group consisting of alkyl, alkylaryl and fatty acyl glyceride groups having 6 to 18 carbon atoms in thealkyl or an acyl group; and M is a water-soluble cation, for example,sodium, potassium, ammonium, for alkylolammonium.

Formula I detergents are disclosed in Volume II of "Surface ActiveAgents and Detergents" and Formula II detergents are described in U.S.pat. Nos. 2,773,068; 2,781,354; and 2,781,357. The acyclic groups may bederived from coconut oil fatty acids (a mixture of fatty acidscontaining 8 to 18 carbon atoms), lauric fatty acid, and oleic fattyacid, and the preferred groups are C₇ to C₁₇ alkyl groups. Preferreddetergents are sodium N-lauryl beta-aminopropionate, disodium N-lauryliminodipropionate, and the disodium salt of2-lauryl-cycloimidium-1-hydroxyl, 1-ethoxyethanoic acid, 1-ethanoicacid.

Cationic surface active agents may also be employed. Such agents arethose surface active detergent compounds which contain an organichydrophobic group and a cationic solubilizing group. Typical cationicsolubilizing groups are amine and quaternary groups.

Examples of suitable synthetic cationic detergents are normal primaryamines RNH₂ wherein R is C₁₂ to C₁₅ ; the diamines such as those of thetype RNHC₂ H₄ NH₂ wherein R is an alkyl group of about 12 to 22 carbonatoms, such as N-2-aminoethyl stearyl amine and N-2-aminoethyl myristylamine; amide-linked amines such as those of the type R₁ CONHC₂ H₄ NH₂wherein R₁ is an alkyl group of 8 to 20 carbon atoms, such as N-2-aminoethylstearyl amide and N-amino ethylmyristyl amide; quaternary ammoniumcompounds wherein typically one of the groups linked to the nitrogenatom is an alkyl group of about 8 to 22 carbon atoms and three of thegroups linked to the nitrogen atom are alkyl groups which contain 1 to 3carbon atoms, including alkyl groups bearing inert substituents, such asphenyl groups, and there is present an anion such as halogen, acetate,methosulfate, etc. The alkyl group may contain intermediate linkagessuch as amide which do not substantially affect the hydrophobiccharacter of the group, for example, stearyl amide propyl quaternaryammonium chloride. Typical quaternary ammonium detergents areethyl-dimethyl-stearyl ammonium chloride, benzyl-dimethylstearylammonium chloride, trimethyl-stearyl ammonium chloride, trimethyl-cetylammonium bromide, dimethyl-ethyl-lauryl ammonium chloride,dimethyl-propyl-myristyl ammonium chloride, and the correspondingmethosulfates and acetates.

Preferred detergent compositions of this invention are the liquid,antimicrobial shampoo compositions suitable for washing the hair andscalp. Such compositions consist essentially of about 10% to 40% byweight of a detergent selected from the group consisting of non-soapanionic, amphoteric, and zwitterionic detergents from 0.1% to 3% byweight of water-soluble or water-insoluble particulate antimicrobialactive material, 0.5% to 3.5% of aminopolyureylene resin, and thebalance primarily water. The shampoo compositions may also include minoramounts of ethanol or isopropanol, perfume, color, stearate opacifyingagents, ethylene diamine tetracetate or citrate sequestering agents,thickening agents, and fatty acid alkylolamide foam boosters.

Other detergent compositions falling within the scope of the inventionare the heavy-duty laundering compositions containing APU polymers andat least one of the active materials potentiated by thepolaminopolyureylene resins, such as antibacterials, fluorescentbrighteners, and bluing agents. Such compositions generally consistessentially of about 8% to 40% by weight of non-soap anionic or nonionicdetergent, about 0.1% to 3% by weight of active material, about 0.5% to3.5% by weight of APU resin and the balance water-soluble inorganic ororganic builder salt. Suitable builders include sodium sulfate, sodiumcarbonate, and sodium nitrilotriacetate as well as the correspondingpotassium compounds. Other compositions are sodiumcarboxymethylcellulose, polyvinylalcohol, perfume, color, etc.

The foregoing laundering detergents may also be prepared in liquid form.Suitable liquids consist essentially of about 5% to 20% by weight ofnon-soap anionic or nonionic detergent, 10% to 25% by weight ofpotassium pyrophosphate, sodium silicate or sodium nitrilotriacetate, 4%to 12% by weight of sodium or potassium xylene or toluenesulfonate, 0.1%to 3.0% by weight of active material, 0.5% to 3.5% by weight of APUresin, and the balance primarily water. Suitable additives which may beadded are sodium carboxymethylcellulose, thickeners, color, and perfume.

In bar form, the detergent material may be soap, anionic, amphoteric,nonionic or mixtures of the foregoing detergents. In addition to theusual proportions of APU resin and active material, the bars may includecolor, perfume, free fatty acids, sodium chloride, and fatty acidalkanolamide suds builders.

Each of the foregoing detergent compositions can be prepared by methodswell known in the art. For example, shampoos and built liquid detergentsare prepared by mixing, and particulate laundering detergents areprepared by mixing, chemical drying or spray drying.

The ability of the APU resins to potentiate the deposition of thewater-insoluble materials which function as antibacterial agents ontoproteinaceous substrates, such as hair and skin, is demonstrated in thefollowing radioactive substantivity test. Substantivity is determined bystirring a 1.27-centimeter diameter circular gelatin disk weighing about40 milligrams for about five minutes in 10 grams of an aqueous mediumcontaining a known concentration of radioactive tagged material such aszinc 2-pyridinethiol-1-oxide, rinsing the disk five times in 10milliliters of water, drying, and measuring the radiation emission withthe aid of a radiation detector. The absolute degree of deposition ofthe material is determined by comparing the observed counts with thecounts emitted by a known weight of the radioactive material. The effectof APU resin on deposition can be readily ascertained by repeating thetest with a known weight of APU present. Similarly, the effect ofdetergents can be quantitatively measured by including detergents in thetest composition.

The following examples are illustrative of the compositions fallingwithin the scope of this invention.

EXAMPLE 1

An aqueous dispersion of zinc 2-pyridinethiol-1-oxide is prepared bydispersing 0.04 grams of radioactive zinc 2-pyridinethiol-1-oxidecontaining zinc 65 in one gram of water. The resultant aqueousdispersion is diluted with 8.96 grams of water with agitation, and thesubstantivity of the diluted dispersion is determined using theforegoing substantivity procedure. The results of the evaluationindicate 40.9 micrograms of zinc-2-pyridinethiol-1-oxide are depositedon the disk from the aqueous mixture containing 0.4% by weight of the2-pyridinethiol-1-oxide. When the foregoing experiment is repeated inthe presence of an amino polyureylene resin (Resin A) having a molecularweight of about 4,300 and the repeating unit ----(CH₂)₃ N(CH₃)(CH₂)₃N(H)C(O)N(H)----, 122 micrograms of zinc 2-pyridinethiol-1-oxide aredeposited on the disk at a concentration of 0.5% of said resin in theaqueous test dispersion. Thus, the presence of 0.5% of APU resin resultsin a 200% increase in the deposition of zinc-2-pyridinethiol-1-oxidefrom an aqueous medium.

Use of a resin having a molecular weight of about 5,600 andN,N'-di(3-aminopropyl) piperazine as the repeating unit in the foregoingtest yields comparable results.

EXAMPLE 2

When the procedure of Example 1 is repeated using an aqueous solution of0.25% by weight of radioactive (C-14) cetyl trimethylammonium bromide(CTAB) at pH 4.5 as the test medium, 294 micrograms of CTAB aredeposited on the gelatin disk. Repetition of this test in the presenceof 0.75% by weight of the APU resin used in Example 1 results in thedeposition of 679 micrograms of CTAB, an increase in deposition of about130%. When the pH of the test solution is increased to 8.5, a depositionof 259 micrograms of CTAB is obtained in the absence of APU resin and adeposition of 734 micrograms is obtained in the presence of 3% by weightof the APU resin of Example 1. Thus, a 180% increase in deposition ofCTAB is noted at pH 8.5.

EXAMPLE 3

Example 2 is repeated with the exception that a 10% aqueous ethanolmixture is substituted for water in the test solution and the pH isadjusted to 6.5. A deposition value of 202 micrograms of CTAB is notedin the absence of APU resin, and a deposition value of 643 micrograms ofCTAB is noted in the presence of 0.75% by weight of the APU resin ofExample 1. This represents an increase in deposition of about 220%. Forcomparison, only 227 micrograms of CTAB are deposited when theconcentration of CTAB in the test solution is increased to 1% by weight.Thus, the APU resin is significantly more effective in enhancingdeposition than an increase in the CTAB concentration from 0.25% to 1%,a 300% increase.

EXAMPLE 4

When the procedure of Example 1 is repeated using a 0.5% by-weightaqueous alcoholic (70%) dispersion of radioactive (C-14) bis(3,5,6-trichloro-2-hydroxyphenyl) methane as the test solution, theradioactivity of the gelatin disk averages 2,100 counts per minute(cpm.) Repetition of the test in the presence of 1.25% concentration ofthe APU resin of Example 1 results in an average radioactivity of 13,200cpm. Thus, the presence of the APU resin increases the deposition of theantimicrobial compound by about 500%. Substantially similar results arenoted when either lamb skin or human callus tissue is substituted forthe gelatin disk in the foregoing experiment.

The APU resin of Example 1 can be replaced by either a resin having amolecular weight of about 4,600 and the repeating unit --CH₂)₃ N⁺ (CH₃)₂(CH₂)₃ NHC(O)NH---- or a resin having a molecular weight of about 6,700and the repeating unit ##STR18## with substantially similar results.Similarly, the substituted methane may be substituted with5-chloro-2(2,4 dichlorophenoxy) phenol with substantially similarresults.

EXAMPLE 5

Tests of the following shampoo illustrate the improved effectsattributable to the APU resin. This shampoo is effective to inhibit thegrowth of Pityrosporum ovale.

    ______________________________________                                                             % by weight                                              ______________________________________                                        Triethanolamine lauryl sulfate                                                                       10                                                     Lauryldimethyl amine oxide                                                                           10                                                     Cocomonoethanol amide  5                                                      Ethyl alcohol          10                                                     Zinc 2-pyridinethiol-1-oxide                                                                         1.6                                                    Resin A.sup.(a)        2.0                                                    Water                  Balance                                                                       100.0                                                  ______________________________________                                         .sup.(a) Aminopolyureylene resin having a molecular weight of about 4,300     and a repeating unit of [(CH.sub.2).sub.3 N(CH.sub.3)(CH.sub.2).sub.3         N(H)C(O)N(H)                                                             

When the foregoing composition is formulated with a radioactive zinc2-pyridinethiol-1-oxide (Zn 65) material and is evaluated using thesubstantivity procedures of Example 1, 20.8 micrograms of radioactivezinc 2-pyridinethiol-1-oxide are noted on the gelatin disk. In thisevaluation, 2.5 grams of shampoo are diluted with 7.5 grams of water tosimulate normal use dilution of shampoos, and the diluted shampoo istest solution. Under such conditions, the concentration of zinc2-pyridinethiol-1-oxide in the test solution is 0.4% by weight, and theconcentration of APU resin is 0.5% by weight. Repetition of the foregingtest with an identical composition not containing APU resin results inthe deposition of 8.7 micrograms of zinc 2-pyridinethiol-1-oxide. Thus,use of APU resin in combination with zinc 2-pyridinethiol-1-oxide in thepresence of detergents results in an increase in deposition of about140%.

To confirm that increased deposition results in enhanced residualactivity, radioactive disks obtained using the foregoing evaluationtechnique are plated in a standard agar medium inoculated with P. ovale,and the diameters of the zone of inhibition are measured aftertwenty-four hours of incubation. These results are shown in Table Itogether with results of nonradioactive disks. Resin A alone has no zoneof inhibition.

                  TABLE I                                                         ______________________________________                                           Zinc                   Zone of inhibition                                  2-pyridinethiol-1-oxide                                                                       APU resin after 24 hours (m.m.)                               ______________________________________                                        Radioactive     No        24.9                                                Radioactive     Yes       40.3                                                Non-radioactive No        20.1                                                Non-radioactive Yes       43.5                                                ______________________________________                                    

The foregoing results indicate that APU resin significantly improves theantibacterial effectiveness of the zinc 2-pyridinethiol-1-oxide.Further, the results show that radioactivity has a minimal effect on theresults.

The effect of APU resin on long-standing activity is illustrated byrepeatedly transferring the radioactivity disks of Table I to freshlyseeded agar plates inoculated with P. ovale for additional incubationperiods after measuring the zone of inhibition. Results are set forth inTable II.

                  TABLE II                                                        ______________________________________                                                Zone of inhibition (m.m.)                                             APU       One         Two         Three                                       Resin     Incubation  Incubations Incubations                                 ______________________________________                                        No        24.9        5.8         0                                           Yes       43.5        24.5        9.4                                         ______________________________________                                    

These results indicate that the presence of APU resin results inimproved antimicrobial effectiveness of the zinc-2-pyridinethiol-1-oxideand longer-lasting effectiveness.

EXAMPLE 6

Example 5 is repeated with the exception that the concentration of zinc2-pyridinethiol-1-oxide in the shampoo is reduced to 0.4%. 17.4micrograms of zinc 2-pyridinethiol-1-oxide are deposited on the disk. Inthe absence of the 2% of APU resin, 6.1 micrograms of zinc2-pyridinethiol-1-oxide are deposited on the disk. Again, APU resinsignificantly enhances the deposit of zinc 2-pyridinethiol-1-oxide on aproteinaceous substrate.

EXAMPLE 7

The following liquid detergent composition is an effective antimicrobialdetergent.

    ______________________________________                                                             % by weight                                              ______________________________________                                        Sodium lauryl triethenoxy ether                                               sulfate                8.0                                                    Lauryl dimethyl amine oxide                                                                          7.5                                                    Sodium 2-pyridinethiol-1-oxide                                                                       2.0                                                    Resin A                1.0                                                    Water                  Balance                                                                       100.0                                                  ______________________________________                                    

When the composition is formulated with radioactive sodium2-pyridinethiol-1-oxide, the zone of inhibition determined as describedin Example 5, the gelatin disk exhibits a halo diameter of 54.2 m.m.when tested against P. ovale. In the absence of APU resin, a halodiameter of 37.5 m.m. is observed. These results show that APU resinimproves the effectiveness of the water-soluble sodium2-pyridinethiol-1-oxide material as well as the water-insolublezinc-2-pyridinethiol-1 oxide.

EXAMPLE 8

Another antimicrobial liquid detergent composition having a pH of 8.2follows.

    ______________________________________                                                               % by weight                                            ______________________________________                                        Cocoamidopropyl dimethyl betaine*                                                                      22.4                                                 Sodium N-(2 hydroxyhexadecyl) methyl taurate                                                           6.0                                                  Sodium hexylbenzene sulfonate                                                                          0.8                                                  Lauryl dimethyl amine oxide                                                                            0.6                                                  Tribromosalicylanilide   1.0                                                  Resin A                  3.0                                                  Water                    Balance                                                                       100.0                                                ______________________________________                                         *Coco corresponds to the mixture of alkyls derived from a middle cut of       coconut oil, that is, 1% C.sub.10, 65% C.sub.12, 27% C.sub.14, and 7%         C.sub.16.                                                                

When the foregoing composition is formulated with a radioactive (C-14tagged) tribromosalicylanilide and the deposition evaluated as describedin Example 1, 1.5 micrograms of antibacterial agent are noted on thegelatin disk. As only 0.5 micrograms are deposited in the absence of theAPU resin, use of the APU resin increases deposit by 200%.

EXAMPLE 9

Substitution of 1% of trichlorocarbanilide for thetribromosalicylanilide in the composition of Example 8 yieldssubstantially similar results.

EXAMPLE 10

A lotion shampoo composition exhibiting effectiveness against P. ovalefollows.

    ______________________________________                                                               % by weight                                            ______________________________________                                        Triethanolamine lauryl sulfate                                                                         12.5                                                 Triethanolamine dodecylbenzene sulfonate                                                               7.8                                                  Diethanolamine soap (19 oleic: 1 coco fatty                                   acid)                    3.0                                                  Lauric-myristic diethanolamide                                                                         4.0                                                  Glycerin                 5.0                                                  Sorbitol                 3.5                                                  Diethanolamine           1.9                                                  Monosodium phosphate     0.5                                                  Sodium chloride          0.2                                                  Formaldehyde             0.1                                                  Resin A                  3.0                                                  5, 7-diiodo-8 hydroxyquinoline                                                                         3.0                                                  Water                    Balance                                                                       100.0                                                ______________________________________                                    

When the foregoing shampoo having a pH of 8.8 is formulated withradioactive 5,7-diiodo-8-hydroxyquinoline (I-125) and the depositionevaluated using the procedure of Example 5, the APU resin results in a220% increase in the deposition of the antimicrobial agent. Improveddeposition is also obtained when the pH of the composition to 7.8.

When the concentration of 5,7-diiodo-8-hydroxyquinoline is reduced to 1%in the composition of Example 10, APU resin achieves a 133% increase indeposition of that agent.

EXAMPLE 11

The following composition is an improved shampoo composition.

    ______________________________________                                                             % by weight                                              ______________________________________                                        Triethanolamine lauryl sulfate                                                                       21                                                     Coconut monoethanolamide                                                                             5                                                      Triethanolamine        0.7                                                    Sodium chloride        0.8                                                    Methyl cellulose       0.9                                                    Ethanol                7.0                                                    Resin A                3.0                                                    Fluorescent agent      1.0                                                    Water                  Balance                                                                       100.0                                                  ______________________________________                                    

When the foregoing composition is formulated with the fluorescent agentslisted in Table III and a 1.25% concentration thereof is used to contacta 1"×1" wool swatch for five minutes, the fluorescent values in TableIII are obtained on the wool swatch after it is rinsed with fiveconsecutive 10-milliliter portions of water and air dried.

                  TABLE III                                                       ______________________________________                                        Fluorescent            Res-   Relative                                        Agent                  in     Fluorescence                                    ______________________________________                                        Disodium 4,4'bis[4-anilino-6-methoxyanilino-                                                         No     11                                              5-triazin-2yl-amino]-2,2'-stilbene                                                                   Yes    12                                              disulfonate                                                                   Quaternized 1-p-(sulfonyl-γ-dimethyl-                                                          No     27                                              aminopropyl amido)-phenyl-3-p-                                                                       Yes    74                                              chlorophenyl-pyrazoline                                                       2-strylnaphth (1,2-d) oxazole                                                                        No     15                                                                     Yes    30                                              Disodium 4,4'bis[4,6-dianilino-                                                                      No     47                                              s-triazin-2yl-amino]-2,2'-stilbene                                                                   Yes    55                                              disulfonate                                                                   Substituted amino-coumarin purchased                                                                 No     87                                              under the trade name "Uvitex SWN"                                                                    Yes    93                                              ______________________________________                                    

The foregoing results show that APU resins improve the brighteningeffectiveness of fluorescent agents of the anionic type (stilbenedisulfonate), nonionic (oxazole) and the cationic type (pyrazoline). Theimprovement noted in fluorescence varies from 7% to 200%.

EXAMPLE 12

The following composition is an improved conditioning shampoo.

    ______________________________________                                                               % by weight                                            ______________________________________                                        C.sub.10 to C.sub.16 alkyl* amidopropyl dimethyl betaine                                               16.0                                                 Triethanolamine lauryl sulfate                                                                         4.0                                                  Lauryl dimethyl amine oxide                                                                            0.5                                                  Polyoxypropylene-polyoxyethylene block                                        copolymer having a hydrophobic molecular                                      weight of 1,750 and containing 20% by                                         weight of polyoxyethylene                                                                              5.0                                                  Condensation product of 1:1 mixture of ethylene                               oxide and propylene oxide on butanol                                          (mol. wt. 4,000)         2.0                                                  Resin A                  q.s.                                                 Ethanol                  1.9                                                  Protein**                q.s.                                                 Water, perfume           balance                                                                       100.0                                                ______________________________________                                         *Alkyl group corresponds to the mixture of alkyls obtained from middle cu     of coconut oil                                                                **Wilson Protein WSPX250 obtained by enzymatic hydrolysis of collagen and     having an average molecular weight of about 1,000                        

The effectiveness of the aminopolyureylene resin in improving theconditioning properties of the protein is shown by the followingprocedure. A bleached hair tress about 2.5 inches (weight 0.55 grams) isplaced in contact with 55 grams of the shampoo composition of Example 12and the contact is maintained for 30 minutes. The hair tress is thenremoved from the shampoo, subjected to five consecutive rinses with 55milliliters of deionized water each time, air dried, and analyzedspectrophotometrically for hydroxyproline. (Hydroxyproline is an aminoacid found in hydrolyzed protein, but not in hair). The protein andaminopolyureylene resin are soluble in the shampoo composition having apH of 7.5 and the test results for the composition are set forth inTable IV.

                  TABLE IV                                                        ______________________________________                                                                    Protein                                           Protein       Resin A       Deposited (1)                                     % by weight   % by weight   % by weight                                       ______________________________________                                        2.2           0             0.08                                              0.55          0             0.08                                              2.2           0.4           0.125                                             0.55          1.0           0.10                                              0.55          3.0           0.08                                              0.055         1.0           0.09                                              ______________________________________                                         (1) Hydroxyproline content expressed as protein.                         

The foregoing tabulation shows that aminopolyureylene resin improves thedeposition of water-soluble protein onto hair and thereby achievesimproved conditioning effects.

Substitution of a benzophenone ultraviolet absorber or a silicone forthe gelatin in Example 12 provides compositions having substantiallysimilar improved effects.

When resins having an average molecular weight in the range of 1,000 to20,000 and a repeating unit of ##STR19## are substituted for the resinin the composition of Example 12, substantially similar results areobtained.

Other compositions exhibiting improved effectiveness because of thepresence of an aminopolyureylene resin therein follow:

EXAMPLE 13

A heavy-duty liquid detergent composition having improved resistance tocolor fading because of ultraviolet light follows:

    ______________________________________                                                             % by weight                                              ______________________________________                                        Sodium tridecylbenzene sulfonate                                                                     10.0                                                   Potassium xylene sulfonate                                                                           8.5                                                    Lauric-myristic diethanolamide                                                                       4.5                                                    Potassium pyrophosphate                                                                              15.0                                                   Sodium carboxymethylcellulose                                                                        0.5                                                    2,4-dihydroxybenzophenone                                                                            0.05                                                   Hydrogenated castor oil                                                                              0.5                                                    Resin A                0.5                                                    Water                  balance                                                                       100.0                                                  ______________________________________                                    

2,2'hydroxy4,4'dimethoxybenzophenone may be substituted for thebenzophenone in the composition of Example 13 with substantially similarimproved effects.

EXAMPLE 14

A built particulate laundry detergent composition exhibiting improvedantibacterial effectiveness has the following composition:

    ______________________________________                                                             % by weight                                              ______________________________________                                        Sodium tridecylbenzene sulfonate                                                                     17.5                                                   Sodium tripolyphosphate                                                                              40.0                                                   Sodium silicate (1Na.sub.2 O:2.35SiO.sub.2)                                                          7.0                                                    Sodium sulfate         23.1                                                   Tribromosalicylanilide 0.4                                                    Resin A                3.0                                                    Sodium carboxymethylcellulose                                                                        0.5                                                    Water                  0.5                                                                           100.0                                                  ______________________________________                                    

Fabrics laundered in the foregoing composition exhibit improvedantimicrobial effectiveness.

EXAMPLE 15

A detergent bar composition exhibiting improved resistance to copperdiscoloration has the following composition.

    ______________________________________                                                             % by weight                                              ______________________________________                                        Sodium N lauryl B iminodipropionate                                                                  8.75                                                   Sodium C.sub.10 to C.sub.20 alkane sulfonate                                                         24.25                                                  Sodium tallow soap     26.40                                                  Sodium tridecylbenzene sulfonate                                                                     7.30                                                   Syrupy phosphoric acid (85%)                                                                         7.30                                                   Stearic Acid           3.60                                                   Benzotriazole          0.5                                                    Resin A                4.0                                                    Water                  balance                                                                       100.00                                                 ______________________________________                                    

Ethylene thiourea may be substituted for benzotriazole in thecomposition of Example 15 with substantially similar results.

While the improved properties appear to be due primarily to enhanceddeposition and/or retention of both water-soluble and water-insolublematerials due to the presence of the aminopolyureylene resin in thecompositions, the actual mechanism is not completely understood.Accordingly, applicant does not wish to be bound by any particularscientific theory or explanation.

While compositions containing APU resin and an active material may beprepared by admixing resin and active material in any suitable manner,in the preparation of detergent containing compositions, improvedeffects are obtained when the resin and active material are premixedbefore admixing with the detergent component.

Although the present invention has been described with reference toparticular embodiments and examples, it will be apparent to thoseskilled in the art that similar results may be obtained when theaminopolyureylene resin is used in combination with a wide variety ofwater-soluble and water-insoluble substances in addition to thosespecifically described.

What is claimed is:
 1. A composition comprising a mixture of anaminopolyureylene resin having a molecular weight in the range of 300 to100,000 and having the following repeating unit:

    --(CH.sub.2).sub.n (X)(CH.sub.2).sub.n NHC(Y)NH--

wherein X is NH, N-C₁ to C₂₂ alkyl, ##STR20## Y is O or S and n is 2 or3; and an active material selected from the group consisting of (I)antimicrobials, (II) tarnish inhibitors, (III) ultra violet absorbers,(IV) fluorescent brighteners, (V) bluing agents and (VI) skin treatingcompounds, the weight ratio of resin to active material being effectiveto improve the properties of the active material and being selected fromthe range of 1:1 to 20:1.
 2. A composition in accordance with claim 1wherein said active material is selected from the group consisting of:(I) antimicrobial agents selected from the group consisting of (A)water-soluble and water-insoluble salts of 2-pyridinethiol-1-oxide; (B)substituted bisphenols having the formula ##STR21## wherein X ishalogen, n is 1-3 and R is an alkylene of 1 to 4 carbon atoms ordivalent sulfur; (C) substituted salicylanilides having the formula##STR22## wherein Y is hydrogen, halogen or trifluoromethyl and Z ishydrogen or halogen; (D) substituted carbanilides having the followingstructure ##STR23## wherein Y is hydrogen, halogen or trifluoromethyl, Wis halogen or ethoxy and W₁ is hydrogen or halogen; (E) mono-higheralkyl quaternary ammonium salts selected from the group consisting of C₈to C₂₂ alkyl isoquinolinium halides, C₈ to C₂₂ alkyl pyridinium halidesand salts having the formula ##STR24## wherein R is C₈ to C₂₂ alkyl, R₂and R₃ are each C₁ to C₃ alkyl, R₄ is C₁ to C₃ alkyl or benzyl and A isselected from the group consisting of chlorine, bromine, iodine andmethosulfate; (F) 5,7-diiodo-8 hydroxyquinoline; (G)1,6-di-(4'-chlorophenyldiguanado) hexane and (H)5-chloro-2(2,4-dichlorophenoxy) phenol; (II) tarnish inhibitors selectedfrom the group consisting of benzotriazole and ethylene-thiourea; (III)ultraviolet absorbers having the formula ##STR25## wherein X, Y and Zare each selected from the group consisting of hydrogen, hydroxy, C₁ toC₈ alkoxy and carboxy, at least one of said X, Y and Z being oxy; (IV)fluorescent brighteners selected from the group consisting of (A)stilbene disulfonates having the formula ##STR26## wherein X is OH,##STR27## ##STR28## (B) quaternized aminoalkyl substituted phenylsulfonamide of aryl pyrazolines having the formula ##STR29## wherein Xis hydrogen; phenyl or halogenated phenyl, with not more than one Xbeing hydrogen, and Y is a quaternized ##STR30## wherein R is C₁ to C₄alkyl and R₁ and R₂ are each selected from the group consisting ofhydrogen and C₁ to C₃ alkyl; (C) oxazoles having the formula ##STR31##wherein A and B are different and represent oxygen and nitrogen, and Rrepresents individually hydrogen, alkyl groups having 1 to 6 carbonatoms, chlorine or fluorine; and (D) aminocoumarins having the formula##STR32## wherein R is hydrogen or C₁ to C₂ alkyl; (V) ultramarinebluing agents; and (VI) skin treating materials selected from the groupconsisting of water-soluble polypeptides having a molecular weight of120 to 20,000 which are derived by hydrolyzing a bone- or skin-derivedcollagen protein and polyethylene oxides having a molecular weight inthe range of 500,000 to 1,000,000.
 3. A composition suitable for use informulating an antimicrobial composition or a hair and skin treatingcomposition consisting essentially of a mixture of aminopolyureyleneresin having a molecular weight in the range of 300 to 100,000 andhaving the following repeating unit:

    --(CH.sub.2).sub.n (X)(CH.sub.2).sub.n NHC(Y)NH--

wherein X is NH,N-C₁ to C₂₂ alkyl, ##STR33## Y is O or S and n is 2 or3; and an active material selected from the group consisting of (I) anantimicrobial agent selected from the group consisting of (A)water-soluble and water-insoluble salts of 2-pyridinethiol-1-oxide; (B)substituted bisphenols having the formula ##STR34## wherein X ishalogen, n is 1 to 3 and R is an alkylene of 1 to 4 carbon atoms ordivalent sulfur; (C) substituted salicylanilides having the formula##STR35## wherein Y is hydrogen, halogen or trifluoromethyl and Z ishydrogen or halogen; (D) substituted carbanilides having the followingstructure ##STR36## wherein Y is hydrogen, halogen or trifluoromethyl, Wis halogen or ethoxy and W₁ is hydrogen or halogen; (E) mono-higheralkyl quaternary ammonium salts selected from the group consisting of C₈to C₂₂ alkyl isoquinolinium halides, C₈ to C₂₂ alkyl pyridinium halidesand salts having the formula ##STR37## wherein R₁ is C₈ to C₂₂ alkyl, R₂and R₃ are each C₁ to C₃ alkyl, R₄ is C₁ to C₃ alkyl or benzyl and A isselected from the group consisting of chlorine, bromine, iodine andmethosulfate; (F) 5,7-diiodo-8-hydroxyquinoline; (G)1,6-di(4'-chlorophenyldiguanado) hexane and (H)5-chloro-2(2,4-dichlorophenoxy) phenol; and (II) a skin treatingmaterial selected from the group consisting of water-solublepolypeptides having a molecular weight of 120 to 20,000 which arederived by hydrolyzing a bone- or skin-derived collagen protein in thepresence of acid, alkali or enzyme and polyethylene oxides having amolecular weight in the range of 500,000 to 1,000,000; the weight ratioof resin to active material being effective to improve the properties ofthe active material and being selected from the range of 1:1 to 20:1. 4.A composition in accordance with claim 2 wherein said resin has anaverage molecular weight in the range of 1000 to 20,000 and in saidrepeating unit Y is O and n is
 3. 5. A composition in accordance withclaim 4 wherein said active material is zinc pyridinethiol-1-oxide.
 6. Acomposition in accordance with claim 4 wherein said active material issodium pyridinethiol-1-oxide.
 7. A composition in accordance with claim4 wherein said active material isbis(3,5,6-trichloro-2-hydroxyphenyl)methane.
 8. A composition inaccordance with claim 4 wherein said active material is cetyl trimethylammonium bromide.
 9. A composition in accordance with claim 4 whereinsaid active material is selected from the group consisting of disodium4,4' bis[4-anilino-6-methoxyanilino-s-triazin-2yl-amine]-2,2' stilbenedisulfonate, disodium 4,4' bis(4,6 dianilino-s-triazin-2yl-amino) 2,2'stilbene disulfonate, quaternized-1-p(sulfonyl-γ-dimethyl aminopropylamido)-phenyl-3-p-chlorophenyl pyrazoline, 2-strylnaphth (1,2-d)oxazole, and 4methyl, 7 diethyl amino coumarin.
 10. A composition inaccordance with claim 3 wherein said active material is saidantimicrobial agent.
 11. A composition in accordance with claim 3wherein said active material is said skin-treating material.
 12. Acomposition in accordance with claim 11 wherein said skin-treatingmaterial is said water-soluble polypeptide.
 13. A composition inaccordance with claim 11 wherein said skin treating material is saidpolyethylene oxide.
 14. A method of improving the deposition and/orretention of an active material on a surface treated with said activematerial comprising contacting said surface in the presence of waterwith a mixture of an active material selected from the group consistingof (I) an antimicrobial agent selected from the group consisting of (A)water-soluble and water-insoluble salt of 2-pyridinethiol-1-oxide; (B)substituted bisphenols having the formula ##STR38## wherein X ishalogen, n is 1 to 3 and R is an alkylene of 1 to 4 carbon atoms ordivalent sulfur; (c) substituted salicylanilides having the formula##STR39## wherein Y is hydrogen, halogen or trifluoromethyl and Z ishydrogen or halogen; (D) substituted carbanilides having the followingstructure ##STR40## wherein y is hydrogen, halogen or trifluoromethyl, Wis halogen or ethenoxy and W₁ is hydrogen or halogen; (E) mono-higheralkyl quaternary ammonium salts selected from the group consisting of C₈to C₂₂ alkyl isoquinolinium halides, C₈ to C₂₂ alkyl of pyridiniumhalides and salts having the formula ##STR41## wherein R₁ is C₈ to C₂₂alkyl, R₂ and R₃ are each C₁ to C₃ alkyl, R₄ is C₁ to C₃ alkyl or benzyland A is selected from the group consisting of chlorine, bromine, iodineand methosulfate; (F) 5,7-diiodo-8 hydroxyquinoline; (G)1,6-di(4'-chlorophenyldiguanado) hexane and (H)5-chloro-2(2,4-dichlorophenoxy) phenol; and (II) a skin treatingmaterial selected from the group consisting of water-solublepolypeptides having a molecular weight of 120 to 20,000 which arederived by hydrolyzing a bone- or skin-derived collagen protein in thepresence of acid, alkali or enzyme and polyethylene oxides having amolecular weight in the range of 500,000 to 400,000; and anaminopolyureylene resin having a molecular weight in the range of 300 to100,000 and having the following repeating unit:

    --(CH.sub.2).sub.n (X)(CH.sub.2).sub.n NHC(Y)NH--

wherein X is NH,N--C₁ to C₂₂ alkyl, ##STR42## Y is O or S and n is 2 or3, the weight ratio of resin to active material being from about 0.06 to20:1 and being sufficient to improve the properties of said activematerial.
 15. A method in accordance with claim 14 wherein said activematerial is said antimicrobial agent.
 16. A method in accordance withclaim 14 wherein said active material is said skin treating agent.
 17. Amethod in accordance with claim 16 wherein said active material is saidwater-soluble polypeptide.
 18. A method in accordance with claim 16wherein said active material is said polyethylene oxide.